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Lattice Energy LLC - Battery energy density - product safety - thermal runaways and ultralow energy neutron reactions - April 14 2016

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Global quest to improve performance drives battery R&D toward ever-higher energy densities. High gravimetric energy density rewards battery users with lighter portable or mobile power sources and longer operating times between recharges. Product safety & reliability could be the hidden costs --- higher energy density is a two-edged sword that cuts both ways. Internal electrical shorts, hot sparks, and catastrophic electric arcs are reducing durability and causing thermal runaways, fires, and even explosions in Lithium-ion batteries. Ultralow energy neutron reactions (LENRs) may be causing some of these extreme events; engineering for LENR effects could potentially help improve future battery safety and durability.

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  • Simple techniques to revive a completely dead battery back to 100% of its original charge capacity (full power) are readily available . Battery Reconditioning Ebook http://zbatteryreconditioning.weebly.com/
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  • Added another new slide 138: electric arcing inside worst-case, Armageddon battery thermal runaway events can raise local temperatures high enough so that if air (78% Nitrogen) entering a dying battery comes into contact with superheated Graphite anode materials, there is a possibility that Dicyanoacetylene (C4N2) will be created. Even more internal runaway heating will occur if produced C4N2 is ignited because it burns with Oxygen in air at 5,000 degrees C, is the hottest-known chemical flame, and will easily melt Tungsten metal (m.p. = 3,422 C).
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  • Added new slides 128-130: Japanese battery scientists (Saito et al., 2011) reported Calcium isotope ratio shift in Graphite cathode of an electrochemical cell; can explain isotopic shift with LENR neutron capture at cathode surface
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Lattice Energy LLC - Battery energy density - product safety - thermal runaways and ultralow energy neutron reactions - April 14 2016

  1. 1. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 1 Battery energy density, safety, and LENRs Contact: 1-312-861-0115 Chicago, Illinois USA lewisglarsen@gmail.com Lewis Larsen President and CEO Lattice Energy LLC April 14, 2016 Global quest to improve performance drives battery R&D toward ever-higher energy densities High gravimetric energy density rewards battery users with lighter portable or mobile power sources and longer operating times between recharges Product safety & reliability could be the hidden costs --- higher energy density is two-edged sword that cuts both ways April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 1
  2. 2. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 2March 23, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 2 Increases in global temperatures and ppm CO2 concentration in our Earth’s atmosphere recently set new all-time records going all the way back to 1880. Could these rates now be accelerating? The relationship between higher temperatures and ppm CO2 is well-established scientifically. As long as societal economic costs are reasonable, it would be beneficial to reduce CO2 emissions associated with many different power generation activities. Green ultralow energy neutron reactions (LENRs) are the only new technology on foreseeable horizon that could enable the “energy miracle” of Bill Gates. Xxxxxxxxxxxxxxxxx April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 2 LENRs = ultralow energy neutron reactions Internal electrical shorts, hot sparks, and catastrophic electric arcs … … are reducing durability and causing thermal runaways, fires, and even explosions in Lithium-ion batteries
  3. 3. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 3 Competition pushing batteries to ever-higher energy density Engineering for LENR effects could help improve battery safety and durability LENRS may cause some of these extreme events Thermal runaways fires and explosions
  4. 4. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 4 Higher battery energy density is a two-edged sword Downside risks: corollary effects of high energy density can potentially reduce battery reliability, durability, and total operating lifetime; at worst, thermal runaway fires and even violent explosions can sometimes occur Upside rewards: high battery energy density enables much smaller size, lower weight, and longer operation between recharges; in E-vehicles enables greater operating ranges Upside rewards versus downside risks April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 4
  5. 5. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 5 Contents Competition pushing batteries to ever-higher energy density ………….…......................…. 6 - 15 Overview of important battery chemistries ..................................................................... 16 - 17 Lithium-based batteries are an integral part of modern life ............................................. 18 - 26 Energy density of batteries has increased ~ 10x in 157 years .......................................... 27 - 33 Next-generation battery chemistries ……......................................................................... 34 - 41 Cost of various battery chemistries and other technologies …......................................... 42 Bernstein projects battery market segments out in 2025……………………………….………. 43 Batteries maturing and approaching technological limits ……………………………………… 44 - 46 Downside risk edge of the energy density sword ……………………..……..….………………. 47 - 53 Examples: battery thermal runaways, fires, and explosions …………………………………... 54 - 62 Overview: battery failure mechanisms and thermal runaway processes …..………………. 63 - 79 Discussion: very high local electric fields >109 V/m on battery microstructures ……….… 80 - 88 More discussion of thermal runaways ………………………………………….....………………. 89 - 95 Ultralow energy neutron reactions (LENRs) ………………………………………..……………. 96 - 115 Comparison of Lithium batteries vs. electrochemical LENRs ………………………..…….. 116 - 117 Electrochemical LENRs: Lithium and Palladium isotopic shifts and transmutation ….… 118 - 122 Japanese battery researchers report isotopic shifts in Lithium (2015) ……................... 123 - 127 Japanese battery researchers report isotopic shifts in Calcium (2011) …….................. 128 - 130 Implications of possibility that LENRs are occurring in batteries .................................. 131 - 143 Conclusions ………………………………………………………………………….…………..….… 144 - 147 Working with Lattice and references to its battery presentations ……………....….…...... 148 - 151
  6. 6. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 6 Energy storage is key component of global energy system Dominant storage technology is chemical batteries that store electricity Companies strive to boost energy density because it increases storage capacity Energy density is the amount of energy stored in a given system or a region of space per unit of mass or spatial volume For chemical batteries, energy density can be expressed either in terms of Watt hours per kilogram (Wh/kg - gravimetric) or Watt hours per liter (Wh/l - volumetric) April 12, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 6 Batteries have become indispensable in modern life
  7. 7. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 7 Energy density of technologies from hydropower to fusion Fig. 7 in “Hydrogen: the future energy carrier” A. Zuttel et al. Phil. Trans. R. Soc. A 368 pp. 3329 - 3342 (2010) Li-ionbattery
  8. 8. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 8 Energy density of technologies from batteries to nuclear Energy density upper bound for today’s battery technology ~1 kWh/kg This estimate was made in 2010; as of 2016 this value has still not been achieved “Hydrogen: the future energy carrier” A. Zuttel et al., Phil. Trans. R. Soc. A 368 pp. 3329 - 3342 (2010) http://rsta.royalsocietypublishing.org/content/roypta/368/1923/3329.full.pdf “Only hydrides and ammonia exhibit an energy density close to that of fossil fuels, as shown in figure 7; all other energy carriers are at least an order of magnitude less dense in energy except for nuclear reactions, i.e. fission and fusion. However, nuclear reactions are stationary, i.e. very system demanding for the application and continuous delivery of power. In addition, fusion is still not carried out in a controlled efficient way in a reactor. The energy density in batteries is very limited (less than 0.2 kWh kg−1 in a Li ion battery today). Furthermore, batteries exhibit time constants in the range of several minutes to hours. The potential for the improvement of current battery technology is estimated to be approximately 1 kWh kg−1. Such an ultimate battery could be derived from the Zn-air battery by replacing the Zn with lithium in a set-up with a non-aqueous electrolyte. New types of batteries, e.g. metal-air, where the energy is stored in metal clusters suspended in a non-aqueous electrolyte combined with an oxygen (air) electrode, have the potential for a significantly increased energy density and the cluster suspension would allow the battery to be refueled.”
  9. 9. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 9 http://simanaitissays.com/2013/03/17/ev-good-news/ Battery energy density is less than Hydrogen or fossil fuels
  10. 10. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 10 Physical sizes of all internal battery structures have shrunk centimeter (1.0 cm) millimeter-scale (.01 cm) micron-scale (.001mm) Baghdad battery ~ 250 BCE? 20th century lead-acid starter battery Contemporary Lithium-ion battery Li-ion jelly roll battery Jelly roll architecture maximizes internal surface area Separators between anode and cathode can be very thinResistant to μ–scale LENRs Huge decrease in distance separating battery anodes from cathodes Lead-acid car batteryAncient battery
  11. 11. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 11 Internal battery structures shrunk to boost energy density Jelly roll architecture and thin separators boosted Li-ion energy density Nanotechnology now utilized by advanced batteries and nano-energetic materials Credit: Scientific Reports 3 paper #2335 (2013) High E-field nm-scale hot spots near interfaces  Battery performance is diffusion-rate-limited through intervening materials and across internal interfaces. To improve this parameter and increase overall energy density of battery cells, researchers invented the “jelly roll” architecture and shrank the thicknesses of dielectric plastic separators located between anode and cathode from centimeters to microns (thousand-fold decrease). To further boost performance and some energy density parameters, batteries are increasingly utilizing nanotechnology and developing many new types advanced battery chemistries, e.g., Lithium-sulfur and Lithium-oxygen  Independently of batteries, technologists working to improve energy density and performance metrics of energetic chemical materials used in thermal igniters, propellants, and certain types of advanced explosives are increasingly utilizing much of the same areas of nanotechnology --- this relatively new area of R&D is called “nano-energetic materials” Credit: Thomann Group at Rice University
  12. 12. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 12 http://lithiumbatteryresearch.com/pdf/Inhomogeneities-and-Durability.pdf “Increasing energy density is a top priority for vehicle batteries since a higher energy density translates directly to a greater range. Current research focuses on new electrode chemistries with higher capacity and voltage, but the energy density is the product of three terms: energy density = charge capacity (Ah/kg) × voltage × mass density (kg/L). The third term offers as great an opportunity to improve energy density as the first two terms. (Volumetric energy density is more important than gravimetric energy density in commercial systems.)” “We review work from our laboratory that suggests to us that most Li-ion battery failure can be ascribed to the presence of nano- and microscale inhomogeneities that interact at the mesoscale, as is the case with almost every material, and that these inhomogeneities act by hindering Li transport. (Li does not get to the right place at the right time.) … We propose new research approaches to make more durable, high energy density lithium-ion batteries.” “Effects of inhomogeneities --- nanoscale to mesoscale --- on the durability of Li-Ion batteries” S. Harris (Lawrence Berkeley National Lab) and P. Lu (General Motors) The Journal of Physical Chemistry C 117 pp. 6481 - 6492 (2013) “Increasing battery energy density is a top priority” Current R&D focuses on new chemistries with higher capacity & voltage
  13. 13. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 13 Series of major battery chemistries from 1859 up to today Lead-acid was invented in 1859; still dominates for auto starter batteries Lithium-based chemistries presently dominate high performance battery products Lithium-sulfur along with Lithium-air are higher energy density challengers to Li-ion http://www.oxisenergy.com/
  14. 14. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 14 Energy densities: batteries versus enzymatic fuel cells Enzymatic fuel cells (EFC) have higher energy densities vs. batteries Early-stage technology: enzymes - not precious metals - are used to oxidize fuels “A high-energy-density sugar biobattery based on a synthetic enzymatic pathway” Z. Zhu et al. Nature Communications 5 #3206 (2014)
  15. 15. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 15 Battery energy densities increased by ~10x over 157 years Achieved by improving battery chemistries; Lithium is dominant today Lead-acid chemistry first invented back in 1859; still used in auto starter batteries http://www.estquality.com/technology
  16. 16. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 16 Comparison of three very important battery chemistries Lead-acid (1859), Lithium Iron Phosphate (1997), and Lithium-ion (1991) Each of these 3 different chemistries now dominates certain segments of markets http://www.datacenterjournal.com/lithiumion-power-data-storage-servers/
  17. 17. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 17 Specifications Li-cobalt LiCoO2 (LCO) Li-manganese LiMn2O4 (LMO) Li-phosphate LiFePO4 (LFP) NMC LiNiMnCoO2 Voltage per cell 3.60 / 3.70V 3.80V 3.30V 3.60 / 3.70V Charge limit 4.20V 4.20V 3.60V 4.20V Cycle life 500–1,000 500–1,000 1,000–2,000 1,000–2,000 Operating temp. Average Average Good Good Specific Energy 150–190Wh/kg 100–135Wh/kg 90–120Wh/kg 140-180Wh/kg Specific Power 1C 10C, 40C pulse 35C continuous 10C Safety Less safe Moderately safe Safest Li-ion Moderately safe Thermal runaway 150°C (302°F) 250°C (482°F) 270°C (518°F) 210°C (410°F) Cost Cobalt cost high Moderate High Moderate In use since 1994 1996 1999 2003 Researchers, manufacturers Sanyo, GS Yuasa, LG Chem Hitachi, Samsung, Toshiba Hitachi, Samsung, Sanyo, GS Yuasa, LG Chem, Toshiba A123, GS Yuasa, BYD, ATL, Lishen, JCI/Saft Sony, Sanyo, LG Chem, GS Yuasa, Hitachi, Samsung Notes High specific energy but limited power; laptops, mobile phones High power, good specific energy; power tools, EVs medical devices High power, mod. energy, rugged and safe, flat discharge curve High specific energy, high power; in tools, e-bikes, EVs Characteristics of 4 common Lithium-ion battery chemistries Source: Battery University (see URL further below) http://batteryuniversity.com/learn/article/possible_solutions_for_the_battery_problem_on_the_boeing_787
  18. 18. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 18 Lithium chemistry enabled batteries with high energy density Generally speaking, in portable electronics markets, batteries having the highest energy densities and duration of electrical power output will usually win price/performance contests in energy storage markets Using 30 lb. DieHard Lead-acid batteries to power 4-ounce Apple iPhones is impractical for end-user customers Utilizing advanced chemistries beyond Lead-acid technology allows more electrical charge to be stored inside a battery casing that is much smaller in volume and weighs vastly less; i.e. with higher volumetric energy density Lower density Lead-acid batteries not practical for small smartphones 30 lbs.
  19. 19. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 19 Lithium-based batteries are an integral part of modern life Very strong competitive pressures to further increase energy densities High level of safety is important because of ubiquitous use in consumer products Credit: Chem511grpThinLiBat
  20. 20. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 20 Lithium-based batteries are an integral part of modern life Lithium-based batteries come in many different chemistries LiFePO4 LiCoO2 LiSOCl2 LiAg2CrO4 LiMnO2 Li-air LiAg2V4O11 LiBi2Pb2O5 LiCuO LiCuCl2 Li(CF)x Li2S LiAg2CrO4 LiCu4O(PO4)2 LiPbCuS LiFeS2 LiFeS2 Li-Cu4O(PO4)2 LiSO2Cl2 LiPbCuS LiBi2O3 Li/AlMnO2 LiFeS Li4Ti5O12
  21. 21. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 21 Vast majority of all such products use chemical batteries for power sources Small portable electronic devices have become a ubiquitous, indispensable part of daily life in modern societies Lithium-based batteries are an integral part of modern life
  22. 22. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 22 Lithium-based batteries are an integral part of modern life Lithium-based batteries come in many different shapes and sizes
  23. 23. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 23 Lithium-based batteries are an integral part of modern life Primary batteries CANNOT be recharged safely (fully discharged only once); secondary batteries are designed to be rechargeable Primary Primary Primary Secondary Secondary
  24. 24. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 24 Lithium ion battery: “A typical lithium-ion rechargeable battery. The battery consists of a positive electrode (green) and a negative electrode (red), with a layer (yellow) separating them. When in use, lithium-ions (Li+, blue) travel from the negative electrode (anode) to the positive (cathode). During charging, the process is reversed and lithium ions are transferred back to the anode.” Conceptual overview of a commercial Lithium-ion battery
  25. 25. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 25 http://www.evwind.es/2015/12/25/growth-in-lithium-ion-batteries-for-the-vehicle-electrification-and-grid-energy-storage-sectors-was-significant-in-2014/55060 Conceptual overview of a commercial Lithium-ion battery
  26. 26. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 26 Microscopic overview: selected portion of Lithium-ion battery “Three-dimensional electrochemical Li-ion battery modelling featuring a focused ion- beam/scanning electron microscopy based three-phase reconstruction of a LiCoO2 cathode” T. Hutzenlaub et al., Electrochimica Acta 115 pp. 131 - 139 (2014) Fig. 3. “The basic working principle of the model during charging of the battery. Lithium stored in the active-material domain is split into cations and electrons. The cations are transported through the electrolyte-filled pore space, across the separator and to the anode. Electrons are transported through the active-material domain (low conductivity) and the carbon-binder domain (high conductivity) to the cathode collector. The collector is electrically connected to the anode which allows recombination of cations and electrons at the anode. The relocation of lithium from the cathode to the anode, and thus the charging of the battery, is driven by an external current source.”
  27. 27. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 27 Computer CPU clock speeds increased over 475x in 34 years Enormous decreases in size with vastly greater raw computing power CPU clock speed of 2016 Apple iPhone 6s+ is 1.9 GHZ or ~475x > Osborne “An Osborne Executive portable computer, from 1982 with a Zilog Z80 4 MHz (0.004 GHZ) CPU, and a 2007 Apple iPhone with a 412 MHz ARM11 CPU; the Executive weighs 100 times as much, has nearly 500 times as much volume, cost ~ 10 times as much (adjusted for inflation), and has ~ 1/100th the clock frequency of the smartphone.” Source: Wikipedia
  28. 28. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 28 Energy density of batteries has increased ~10x in 157 years Nadim Maluf, CEO of Qnovo, comments about battery energy densities http://qnovo.com/category/chemistry/ “So by now, you are probably disappointed about the future of batteries! It is true that the progress of batteries over the last 150 years has been slow, and it is true that batteries can’t yet compete with carbon-based fuels … Yes, they can be better, but present batteries boasting 700 Wh/l can and are sufficient to provide an electric vehicle with a range of 300 miles. In other words, don’t expect miracles in batteries, but do expect that incremental technologies from materials to algorithms and electronics will be sufficient to address a wide range of energy storage needs, including smartphones that can last an honest day to electric vehicles with a range of 200 - 300 miles.”
  29. 29. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 29 Energy density of batteries has increased ~10x in 157 years Nadim Maluf, CEO of Qnovo, comments about battery energy densities Tesla claims to be able to double (2x) volumetric energy density over 10 years http://qnovo.com/category/chemistry/ “The third observation: Energy density increased by a factor of 10X over 150 years! That’s not terribly promising unless the future brings forth some serious breakthroughs in materials. Is there anything on the horizon? There is a lot of promising good material research, but when one takes into account cost, cycle life, and other constraints such as manufacturing and capital, it is very hard to point to one particular technology that is likely to be commercialized in the next 5 years. So the wait and the hope continue.” “The fourth observation: Lithium-ion technologies, first commercialized by Sony in 1991, encompass a wide range of energy densities depending on the particular choice of material for the electrodes. Lithium-ion batteries using nickel-cobalt-aluminum oxide (NCA) electrodes --- the type used in the Tesla Model S --- have over 3X the energy density of lithium-ion batteries with lithium iron-phosphate (LFP) electrodes. So why is anyone considering LFP lithium-ion batteries: cycle life! Welcome to the world of compromises.”
  30. 30. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 30 Battery cost/kwh to store electricity has declined greatly over 157 years Idealized relationship between direct cost/unit and total cumulative unit production http://en.wikipedia.org/wiki/Experience_curve_effects An experience curve, which differs somewhat from a so-called “learning curve,” is a graphical representation of a price phenomenon that was developed and widely publicized as a corporate strategy tool by Bruce Henderson, founder of the Boston Consulting Group. Concept refers to effect that manufacturers learn from doing, which means that the higher the cumulative volume of production, the lower the direct cost per new unit of produced product. Thus, experience curves are innately convex and have downward slopes, as shown in two graphs below: Experience curve effect reduces product costs over time
  31. 31. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 31 $ cost/megawatt for steam turbines dropped as unit volumes increased Empirical data shows that it applies to many different manufactured products Total direct cost per megawatt (constant $) vs. total cumulative megawatts for steam turbines sold and delivered by three major OEM manufacturers http://vectorstudy.com/management-theories/experience-curve “Decrease in costs associated with production of steam turbine generators trend towards a line with constant slope on a log-log plot; each data point represents one year.” Effectively the passage of time Experience curve cut costs of producing & storing electricity
  32. 32. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 32 Cost reductions/time will decrease as a technology matures Lithium-ion battery chemistry has ridden experience curve for 25 years http://tingilinde.typepad.com/starstuff/2009/05/the-historic-price-of-electricity-in-the-us.html By 1910, price of electricity was ~$1.60 per kWh (1990 dollars); from 1920s through mid-1930s It mostly averaged around $0.60 kWh; today, price of electricity ranges from ~ $0.05 to 0.12 kWh (1990 dollars) 1970 Real price of electricity flattened-out after very rapid increases in % efficiency of electric power plants ceased around 1970 Average efficiency of coal-fired power plants stagnated at ~32 - 34% since 1960
  33. 33. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 33 Tesla claims it can double battery energy density in 10 years e.g. Tesla increased 90D battery’s capacity 6% by tweaking cell chemistry
  34. 34. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 34 Lithium-sulfur and Lithium-air have higher Wh/kg vs. Li-ion Battery manufacturers focus R&D on increasing battery energy densities http://www.datacenterjournal.com/lithiumion-power-data-storage-servers/ Brave new world of higher battery energy densities Graphic adapted by Lattice
  35. 35. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 35 http://www.nature.com/polopoly_fs/1.14815!/menu/main/topColumns/topLeftColumn/pdf/507026a.pdf Next-generation chemistries: Lithium-sulfur and Lithium-air Lithium-ion technology is nearing energy-density limits for that chemistry “Abetterbattery---Chemistsarereinventing rechargeablecellstodrivedowncostsand boostcapacity”R.VanNoorden NatureNewsMarch5,2014
  36. 36. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 36 Next-generation chemistries: Lithium-sulfur and Lithium-air “Abetterbattery---Chemistsarereinventing rechargeablecellstodrivedowncostsand boostcapacity”R.VanNoorden NatureNewsMarch5,2014
  37. 37. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 37 Lithium-sulfur is possible successor to Li-ion technology Oxis claims gravimetric energy density of 400 Wh/kg; Li-ion is ~200 Wh/kg http://www.hybridcars.com/oxis-jump-starts-first-commercialization-of-lithium-sulfur-batteries/ http://cleantechnica.com/2015/07/01/oxis-manufacture-li-s-batteries-achieving-400-whkg/
  38. 38. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 38 Lithium-air widely touted as next great thing in batteries Fig. 1 from: “Challenges and opportunities of nanostructured materials for aprotic rechargeable lithium-air batteries” J. Wang, Y. Li, and X. Sun, Nano Energy 2 pp. 443 - 467 (2013) Some have even made claims that it may rival gasoline’s energy density
  39. 39. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 39 Lithium-air widely touted as next great thing in batteries Much of IBM’s work in Li-air technology conducted in Battery 500 project http://www.ibm.com/smarterplanet/us/en/smart_grid/article/battery500.html Credit: IBM Quoting from IBM webpage: “During discharge (driving), oxygen from the air reacts with lithium ions, forming lithium peroxide on a carbon matrix. Upon recharge, the oxygen is given back to the atmosphere and the lithium goes back onto the anode.”
  40. 40. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 40 Two major players in Lithium-air batteries curb R&D efforts IBM and the Joint Center for Energy Storage Research (JCESR) “In a sign of more gloom in the struggle for a better battery, two major US labs have quietly downgraded research on a technology until now widely believed to be the most promising path to a competitive electric car.” “IBM and the US-funded Joint Center for Energy Storage Research (JCESR) have ratcheted down or outright abandoned their work on the lithium-air battery, a concept in which oxygen would react with lithium to create electricity.” “In a little-remarked-upon article in March, Nature magazine reported that IBM’s Winfried Wilcke, director of the Battery 500 Project, had a ‘change of heart’ about lithium-air and had turned his favor to a technology featuring sodium. In an electric car, a sodium-air battery, he said, stood a better chance of meeting the economics needed to compete with conventional cars. It was a dramatic move, with the most bullish player in lithium-air --- Wilcke himself --- calling it a day.” http://qz.com/214969/two-big-labs-most-promising-next-generation-battery-electric-car/ “Two big labs step back from the most promising next-generation battery” Steve Levine in Quartz May 30, 2014
  41. 41. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 41 http://qz.com/214969/two-big-labs-most-promising-next-generation-battery-electric-car/ Two major players in Lithium-air batteries curb R&D efforts IBM and the Joint Center for Energy Storage Research (JCESR) “Two big labs step back from the most promising next-generation battery” “Wilcke did not respond to emails. An IBM spokesman told Quartz that the Nature report is accurate but said that the company is now working on both lithium-air and sodium.” “About the same time, JCESR dropped its lithium-air project entirely. Like IBM, JCESR did not announce the decision publicly. Kevin Gallagher, a JCESR manager, said it concluded that the challenges were too overwhelming to resolve any time soon. ‘The penalty of using gaseous reactions overwhelmed any advantage,’ he told Quartz.” “Lithium-air is not being abandoned everywhere. At Argonne, Michael Thackeray is directing work on a novel hybrid battery combining lithium- ion and lithium-air. The result is the potential for a battery with specific density of 500 watt hours per kilogram, two-and-a-half times greater than today’s best commercial lithium-ion cell.” Steve Levine in Quartz May 30, 2014
  42. 42. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 42 Cost of various battery chemistries and other technologies Vanadium redox flow battery is most expensive; thermal storage cheapest http://www.theenergycollective.com/jayirwinstein/2279921/who-s- reserving-all-those-tesla-batteries-and-what-do-they-plan-using-them
  43. 43. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 43 Bernstein projects battery market segments out in 2025 Foresees increased dominance of Lithium-ion chemistry in near-future Seems to be implying that Li-ion will steal market share from Lead-acid chemistry
  44. 44. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 44 http://www.nature.com/news/the-rechargeable-revolution-a-better-battery-1.14815 What lies for future batteries beyond today’s Lithium-ion? Lithium-ion technology is nearing energy-density limits for the chemistry “A better battery --- Chemists are reinventing rechargeable cells to drive down costs and boost capacity” R. Van Noorden in Nature News March 5, 2014 “Modern Li-ion batteries hold more than twice as much energy by weight as the first commercial versions sold by Sony in 1991 --- and are ten times cheaper. But they are nearing their limit. Most researchers think that improvements to Li-ion cells can squeeze in at most 30% more energy by weight. That means that Li-ion cells will never give electric cars the 800-kilometre range of a petrol tank, or supply power-hungry smartphones with many days of juice.” http://www.nature.com/polopoly_fs/1.14815!/menu/main/topColumns/topLeftColumn/pdf/507026a.pdf
  45. 45. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 45 http://www.nature.com/articles/nenergy201520 Battery cost reduction tied to increases in energy density If energy density increases slow down then cost reductions will stagnate Fig. 3 in “The frontiers of energy” R. Armstrong et al. Nature Energy 1 Article # 15020 (2016)
  46. 46. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 46 Note: superimposed S-curve added by Lattice Batteries maturing and approaching technological limits We predict energy density increases and cost reductions will slow down http://www.estquality.com/technology Adapted from original source by Lattice Next 10 -15 years
  47. 47. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 47 Downside risk edge of the energy density sword Caution is merited: battery capacity scale-up can increase safety risks Runaways in tiny batteries have limited effects; big packs can cause loss-of-life  Thermal runaway event inside a single-cell, Lithium-based ‘button’ battery might ruin a small electronic device, but it probably won’t set anything else on fire or hurt any nearby person or persons seriously  Runaway inside smartphone’s multi-cell battery might start a woman’s handbag smoking or burn a hole through a man’s pants pocket, or make someone drop it, but it generally would not cause serious skin burns or ignite a large portion of someone’s clothing  Catastrophic runaways inside significantly larger, multi-cell laptop computer batteries have inflicted serious burns on people’s legs and in several documented cases, have even burned-down entire homes  Runaways involving large to extremely large many-cell secondary batteries on stationary (onsite back-up power) and mobile platforms such as hybrid or all-electric vehicles and passenger or cargo aircraft are very serious matters; can cause multiple fatalities and up to many millions of $ in physical damage to equipment and/or local facilities Riskscanincreasewithscale-up
  48. 48. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 48 Downside risk edge of the energy density sword On rare occasions batteries can have problems that create product safety risks Devices with high chemical or electrical energy densities can be risky While detonations of individual energy-dense, Lithium-based battery cells are extremely rare events, they can be nearly as powerful as exploding dynamite Would you play with this?
  49. 49. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 49 Downside risk edge of the energy density sword Risks for thermal runaways, hot fires, and catastrophic explosions Spontaneous Lithium battery fires and explosions have occurred with e-cigarettes All of these injuries occurred very recently with e-cigarettes or vaping devices Google under “images” and see horrific injuries Good news is that nobody has been killed … yet E-cigarette Larger vaping device
  50. 50. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 50 Downside risk edge of the energy density sword Risks for thermal runaways, hot fires, and catastrophic explosions Spontaneous Lithium battery fires and explosions have occurred with e-cigarettes Small Lithium-based batteries in e-cigarettes and vaping devices can cause horrific injuries when they suffer catastrophic spontaneous thermal runaways
  51. 51. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 51 Downside risk edge of the energy density sword Risks for thermal runaways, hot fires, and catastrophic explosions Laptop OEMs have had recalls for battery problems; some houses burned down Other example 2 - credit: Shmuel De-Leon Other example 3 Other example 4 http://www.westernmassnews.com/story/31624627/fire-destroys-wilbraham-home-after-laptop-battery-explosion “Fire destroys Wilbraham home after laptop battery explosion” By Maggie Lohmiller and Ryan Trowbridge, Western Mass News, posted: Apr 01, 2016 6:10 PM CDT Updated: Apr 01, 2016 6:10 PM CDT
  52. 52. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 52 Downside risk edge of the energy density sword Risks for thermal runaways, hot fires, and catastrophic explosions Laptop OEMs have had recalls for battery problems; some houses burned down http://money.cnn.com/2016/04/01/technology/toshiba-laptop-battery-recall-panasonic/ “Toshiba recalls 100,000 batteries that can melt your laptop” By Aaron Smith, CNN, posted: Apr 01, 2016 6:10 PM CDT “Toshiba is recalling faulty laptop batteries that are too hot to handle. The lithium-ion battery packs, which are made by Panasonic, can overheat, posing burn and fire hazards to consumers, according to the U.S. Consumer Product Safety Commission on Thursday.” “Toshiba received four reports of the battery packs overheating and melting, though the CPSC said no injuries have been reported.” “Toshiba, which first announced the recall in January, said it was recalling the batteries in certain Toshiba Notebook computers sold since June 2011. The Japanese manufacturer said it would replace them for free.” “The CPSC said the recall involves 91,000 laptops sold in the United States and 10,000 sold in Canada. The recall involves 39 models of Portege, Satellite and Tecra laptops.”
  53. 53. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 53 Downside risk edge of the energy density sword Risks for thermal runaways, hot fires, and catastrophic explosions Spontaneous Lithium battery thermal runaways and fires occur in hoverboards
  54. 54. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 54 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems “All of the batteries that were involved in the accidents reported in [6–9] have high capacity and large formats in dimension. Large format batteries are favored by manufacturers because they reduce the cell number and pack complexity in battery pack design [10], thereby improving the reliability of a battery pack [11]. However, a large format battery is more vulnerable to safety problems because it contains more stored energy. Cooling is less effective because of the lower surface/volume ratio, which leads to higher non-uniformity in the temperature distribution within the cell [11]. A local hot spot, which may be triggered by an internal short circuit (ISC), can propagate throughout the whole cell, resulting in thermal runaway and fire [11]. An ISC is believed to be the root cause of the large format lithium ion battery fire in a series of accidents of Boeing 787 Dreamliner airplanes [8,9]. In those cases, local heat generation, induced by the ISC, developed into thermal runaway in one of the large format batteries, resulting in cell-to- cell propagation and subsequent failure of the whole battery pack [8,9].” “Online internal short circuit detection for a large format lithium ion battery” X. Feng et al. Applied Energy 161 pp. 168 - 180 (2016) http://www.umich.edu/~racelab/static/Webpublication/2016-ENERGY-XuningF.pdf
  55. 55. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 55 http://www.youtube.com/watch?v=TzPv9ptIXNI During 2011 several suspicious, rather frightening fires occurred in Renault F1 race cars equipped with Li-ion batteries in the cars’ KERS (kinetic energy recovery system); the Saft Li-ion batteries used in the 2011 season’s Renault Formula 1 (F1) KERS most likely had Lithium iron phosphate (LIPO) chemistry Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems
  56. 56. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 56 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems 2013: freeze-frame from amateur video of incident shows entire front-end of Tesla Model S completely engulfed in flames http://www.youtube.com/watch?feature=player_embedded&v=q0kjI08n4fg
  57. 57. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 57 2015 Tesla Model S P90D --- MSRP as configured is roughly $121, 950 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems 691hp 90 kWh lithium-ion
  58. 58. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 58 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems July 12, 2013: battery fire broke out on an empty Ethiopian Airlines 787 sitting on ground Investigators concluded that this fire was likely caused by Lithium-manganese dioxide primary batteries powering a small Honeywell emergency locator transmitter beacon in the roof area Some claimed to explain this battery fire was result of “crimped wires” inside Honeywell locator beacon rather than caused by spontaneous internal field-failure of some kind Top viewSide view Battery fire burned through Carbon-fiber skin
  59. 59. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 59 Credit: NTSB UPS 747-400 Boeing cargo plane caught fire due to Lithium-ion batteries carried in onboard cargo - Dubai Sept. 5, 2010 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems
  60. 60. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 60 Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions
  61. 61. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 61 Severely fire-damaged aft Boeing787 GS-Yuasa Li-ion backup battery (NTSB) Boeing 787 Dreamliner (aft electronics bay) Boston Logan Airport Lithium-ion battery fire (2013) Since it began flying passengers on Oct. 26, 2011, brand-new Boeing 787 Dreamliners have experienced at least two different thermal runaway incidents involving GS-Yuasa Lithium-ion system backup batteries: first with JAL while on the ground in Boston (Logan) and second with ANA on domestic flight in Japan Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions Spontaneous Lithium battery thermal runaways have occurred in large systems
  62. 62. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 62 Advanced seal delivery system (ASDS) all-electric minisub was designed to covertly transport U.S. Navy SEAL teams to land targets from nuclear submarines hidden underwater > 100 miles offshore At the time of test sea-trials in Hawaii, ASDS had highest-capacity Lithium-based battery pack ever built until then: 1.2 megawatts. In November 2008, while sitting overnight on dry dock being inspected and then recharged, the ASDS minisub was destroyed by a still unexplained battery fire with massive explosions. U.S. Navy cancelled entire ASDS program shortly thereafter without any explanation Yardney ASDS 1.2 MW battery pack Runaways in battery packs or cargo can destroy big systems Risks for thermal runaways, blazing fires, even catastrophic explosions
  63. 63. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 63 Chemical batteries: very safe energy storage technology In statistical terms, severe thermal runaways are extremely rare events Nonetheless they must be mitigated as much as possible to prevent human injury  By any reasonable standard, Lithium-based batteries are a very safe technology; ‘garden variety’ thermal runaways only occur at frequencies of one failure event per several million battery cells  Very worst, often catastrophic, and least understood type of thermal runaway goes under the innocuous-sounding sobriquet of “field-failure.” According to statistics collected over a long time period by a major Japanese manufacturer of Lithium-ion consumer batteries, field-failures seemingly occur at rates of one such event per ~ 4 - 5 million fresh Lithium-based battery cells that come right off the production line, regardless of their chemistry or whether a battery is primary versus secondary  One more related issue: although it is admittedly difficult to specify quantitatively, the probability of field-failure thermal runaway events appears to increase significantly as batteries ‘age’ and go thru a great many charge-discharge cycles; however, not all battery chemists agree with that contention
  64. 64. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 64 Positive temp feedback loop creates thermal runaways Lithium-ion battery cells have a relatively small safe operating window ~325 oC Thermal runaway + feedback loop Voltage/temp safe operating window only occupies small portion of entire battery parameter space Catastrophic thermal runaways can be created by temperatures as low as 325 oC Danger zone starts at ~ 100o C Destabilizing breakdown of crucial SEI layer begins at ~ 100o C
  65. 65. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 65 Barnett et al: peak temperatures in battery thermal runaways Different maximums are reached depending on exactly what happens 1825o C for 100% electrolyte combustion; far higher temps with electric arcs “Batteries for Sustainability – Selected Entries from the Encyclopedia of Sustainability in Science and Technology”, Ralph J. Brodd, ed., Springer ISBN 978- 1-4614-5791-6 (eBook) 519 pages (paper); see Chapter 9 by B. Barnett et al., “Lithium-ion Batteries, Safety” Springer (New York) 1 edition (2012) US$143.50 Circa 460o C is a typical value for the auto-ignition temperature of many different battery solvents Theoretical calculations from Fig. 9.1 in Barnett et al. (2012). With thermal runaway in a commodity 18650 Li-ion cell, and depending on exactly what happens in such a cell, peak temperatures during an event can range from 300 up to 1,825o C
  66. 66. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 66 Temperatures in some thermal runaways can exceed 3,000o C Internal shorts can lead to electric arcs in catastrophic battery failures Steel microspheres in SEM images of battery debris after thermal runaway Lattice has concluded that presence of perfect stainless steel microspheres in debris of the ruined GS Yuasa battery implies local temperatures must have reached > 3,000o C. Such tiny microspheres are created by condensation of droplets from a vapor phase; identical types of microspheres are produced when metals are subjected to high-intensity laser pulse ablation NTSB Report No. 13-013 NTSB Report No. 13-013 NTSB report indicated extremely high local internal temperatures (2013) Data suggests that temperatures above 3,000o Centigrade likely occurred at local hotspots created by high-current electric arcs occurring inside a GS Yuasa Lithium battery during Boeing Dreamliner thermal runaway event at Boston Logan airport
  67. 67. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 67 Inner cores of electric arcs can hit monstrous temperatures Refractory metals will be melted and other materials will be combusted April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 67
  68. 68. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 68 What factors are involved in triggering thermal runaways? Complex: many different things can contribute to battery thermal failures http://www.ntsb.gov/news/events/Documents/2013_Lithium_Batteries_FRM-Panel1d-Doughty.pdf “Failure mechanisms of Li-ion batteries” Dr. Daniel Doughty, Battery Safety Consulting, Inc. NTSB Battery Forum 12 MS-PowerPoint slides April 11, 2013
  69. 69. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 69 Sequence of events associated with thermal runaways Battery systems design and engineering can steer toward safe outcome http://www.ntsb.gov/news/events/Documents/2013_Lithium_Batteries_FRM-Panel1d-Doughty.pdf “Failure mechanisms of Li-ion batteries” Dr. Daniel Doughty, Battery Safety Consulting, Inc. NTSB Battery Forum 12 MS-PowerPoint slides April 11, 2013
  70. 70. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 70 Overview of degradation mechanisms in Lithium batteries http://epg.eng.ox.ac.uk/content/degradation-lithium-ion-batteries Includes the formation of metallic dendrites and internal short circuits Fig. 1: “Degradation mechanisms in Li-ion batteries” in Christoph Birkl’s blog article
  71. 71. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 71 High electric field gradients near battery electrode surfaces Voltage gradient quite high because distance involved is very small Fig. 8. “(a) The formation of a double layer constituted from an increased concentration of oppositely charged ions on a positive electrode is shown. The spatial extent of the Helmholtz layer is dependent on the character of ions (cations and anions, the degree if solvation). (c) The distribution of the mobile charges in the metal electrode (on the left) and the electrolyte (on the right). (d) Much of the applied voltage on the electrode is dropped across the immobile Helmholtz layer.” “Charge transfer and storage in nanostructures” P. Bandaru et al. Materials Science and Engineering R 96 pp. 1 - 69 (2015)
  72. 72. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 72 High electric field gradients near battery electrode surfaces Localized electric field strengths of 109 - 1010 V/m near electrode surfaces Inhomogeneities in electric field strengths or current densities are very important “A multiscale model of electrochemical double layers in energy conversion and storage devices” M. Quiroga et al., Journal of The Electrochemical Society 161 pp. E3302-E3310 (2014) Fig. 3 Quiroga et al. - Simulated electrode/electrolyte interface in a Lithium-ion battery High electric fields occur near battery anode and cathode surfaces. Sudden mechanical changes (fracture) or drastic shifts in electron/ion currents interacting with these fields can boost dendrite growth, cause brief charge separation, destabilize SEIs, and trigger LENRs
  73. 73. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 73 Battery electrode double layer has steep E-field gradient See E. Stuve’s article titled “Interfacial chemistry in high electric fields” High electric fields at cathode surfaces in electrochemical cells; DFT model of double-layer http://faculty.washington.edu/stuve/fi_water.htm Fig. 2. DFT/molecular dynamics simulation of a charged Pt(111) slab with 3 water layers Quasi-static electric field strengths of ~ 1010 V/m occur very close to double layer “Density functional theory (DFT) model of Fig. 2, for three water layers and one hydronium ion (dark blue/orange) at a Pt(111) surface, focuses on the adsorbed or near-surface layer. The water molecules alter their orientation in response to the hydronium ion. The red curve shows the potential profile, and the blue curve is the field profile obtained by differentiating the potential profile. The field profile varies from zero in the metal, to a maximum of 1 V/Å near the surface, and to zero into the solution phase. There is an appreciably wide region where the field exceeds 0.3~V/Å, at which water ionization is possible, according to work in our laboratory. Comparison of this experimental result with the computational result shows that ionization would be expected to occur over the range where the field exceeds the ionization threshold, from 1.5 to 3.5 V/Å from the surface.”.
  74. 74. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 74 Electrode/electrolyte interface is still not well understood Knowledge about SEI at Li battery anodes is much better than cathodes Ramifications of very high electric fields in vicinity of EEI are extremely important http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.5b01727?journalCode=jpclcd Abstract: “Understanding reactions at the electrode/electrolyte interface (EEI) is essential to developing strategies to enhance cycle life and safety of lithium batteries. Despite research in the past four decades, there is still limited understanding by what means different components are formed at the EEI and how they influence EEI layer properties. We review findings used to establish the well-known mosaic structure model for the EEI (often referred to as solid electrolyte interphase or SEI) on negative electrodes including lithium, graphite, tin, and silicon. Much less understanding exists for EEI layers for positive electrodes. High-capacity Li-rich layered oxides yLi2–xMnO3·(1–y)Li1–xMO2, which can generate highly reactive species toward the electrolyte via oxygen anion redox, highlight the critical need to understand reactions with the electrolyte and EEI layers for advanced positive electrodes. Recent advances in in situ characterization of well-defined electrode surfaces can provide mechanistic insights and strategies to tailor EEI layer composition and properties.” “Electrode - electrolyte interface in Li-ion batteries: current understanding and new insights” M. Gauthier et al. Phys. Chem. Lett. 6 pp. 4653 - 4672 (2015)
  75. 75. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 75 SIMS mass spectroscopy is a very powerful analytical tool Cameca nanoSIMS-50L is outstanding instrument to look for LENR traces Abstract: “Dynamic structural and chemical evolution at solid-liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe a solid-liquid interface under reaction conditions. We describe the creation and usage of in situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid-liquid electrolyte interface for a Lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to be depleted of the salt anions and with reduced concentration of Li+ ions, essentially leading to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributing to the overpotential of the cell. This observation provides unprecedented molecular level dynamic information on the initial formation of the solid electrolyte interphase (SEI) layer. The present work also ultimately opens new avenues for implanting the in situ liquid SIMS concept to probe the chemical reaction process that intimately involves solid-liquid interface, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization.” http://pubs.acs.org/doi/abs/10.1021/acs.nanolett.5b02479?src=recsys&journalCode=nalefd “In situ mass spectrometric determination of molecular structural evolution at the solid electrolyte interphase in Lithium-ion batteries” Z. Zhu et al. Nano Lett. 15 pp 6170 - 6176 (2015)
  76. 76. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 76 SIMS mass spectroscopy is a very powerful analytical tool Cameca nanoSIMS-50L is outstanding instrument to look for LENR traces Note electron-rich (surface plasmon) environment on the surface of Copper (Cu) http://pubs.acs.org/doi/abs/10.1021/acs.nanolett.5b02479?src=recsys&journalCode=nalefd
  77. 77. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 77 http://lithiumbatteryresearch.com/pdf/Inhomogeneities-and-Durability.pdf “Effects of inhomogeneities --- nanoscale to mesoscale --- on the durability of Li-ion batteries” S. Harris (Lawrence Berkeley National Lab) and P. Lu (General Motors) The Journal of Physical Chemistry C 117 pp. 6481 - 6492 (2013) “Inhomogeneities in batteries --- just like inhomogeneities in practically all materials --- are the primary drivers of failure, so that in at least some cases, a purely homogeneous model will not be able to predict durability. Instead, we suggest that a detailed understanding of the electrode structures and inhomogeneities at all scales, from nano- to mesoscale (where inhomogeneities interact), can lead to an improved understanding of durability and failure mechanisms, ultimately leading to longer-lived batteries, with all their attendant advantages.” “Materials do not in general fail homogeneously; instead, nano- and microscale inhomogeneities interact at the mesoscale to cause failure. We hypothesize that battery failure is the result of interactions among local inhomogeneities --- mechanical, electrical, morphological, or chemical. (For the purposes of our work, we define inhomogeneities as regions with sharply varying properties --- which includes interfaces --- whether present by ‘accident’ or design.)” Explains how inhomogenities can impact battery durability
  78. 78. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 78 State of charge [SOC] is really not homogenous on nanoscales “Effects of inhomogeneities --- nanoscale to mesoscale --- on the durability of Li-ion batteries”, Harris & Lu (2013) continued “Until recently, there were no in situ Li maps, no in situ strain maps, no 3D electrode or particle data, no models dealing with real 3D data, no determinations of how Li transports through the SEI, and in general only a very modest interest in how nano- and microscale inhomogeneities might interact to cause failure at the mesoscale.” “Maire et al. showed a graphite electrode that failed heterogeneously, with variations in SOC [state of charge] on a scale of millimeters. Such heterogeneous failure suggests different remediation strategies than would homogeneous failure … The isotropy assumption predicts that the state of charge [SOC] on the surface of a spherical particle must be uniform. That translates to a prediction for spherical graphite particles that their external surfaces are monochromatic (gray/black, blue, red, or gold). Our in situ optical images of lithiating ∼10 μm spherical mesocarbon microbeads (MCMBs) show instead that particles lithiate gradually from ‘hot spots’ that expand over the surface until they cover the particle (Figure 3). This observation is readily rationalized using a microstructural model of MCMB particles in which the hot spot location depends on the internal microstructure of the graphite.” Explains how inhomogenities can impact battery durability
  79. 79. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 79 Explains how inhomogenities can impact battery durability “Effects of inhomogeneities --- nanoscale to mesoscale --- on the durability of Li-ion batteries”, Harris & Lu (2013) continued “There is little experimental information about Li transport mechanisms through the SEI --- how the SEI actually functions --- although at least three different mechanisms have been proposed. In addition, we are not aware of any measurements of the electrical conductivity of an SEI film, which ideally should be zero but is clearly not, since SEI films inevitably grow. In fact, while tunneling is commonly invoked as a mechanism for electron transport through the SEI, a thickness of 10 or 20 nm indicates that it must be combined with other mechanisms, as suggested by Qi. To understand battery degradation, we need mechanistic information about how SEI films fail … TOF-SIMS depth profiles show that this outer SEI region is composed largely of polymeric and organic Li salts, chemically distinct from the more inorganic region below it.” “Homogeneous porous electrode models have provided invaluable tools for improving the performance of Li-ion batteries, but the model was not designed to predict durability. We propose that degradation be understood by explicitly considering effects --- beneficial or deleterious --- of local inhomogeneities on Li+ transport at larger scales. The value of this hypothesis, if true, is that it gives a straightforward prescription for making more durable batteries: control the number and intensity of heterogeneities. While this approach is widely used to make other materials more durable, it is not discussed in the context of Li-ion battery failure.”
  80. 80. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 80 High electric fields foster Lithium metal dendrite growth Electric fields are concentrated and much higher on tips of dendrites Enhancement of electric field strengths also occurs on spherical nanoparticles  Role of metallic Lithium dendrites in battery failures is well-known and much R&D has consequently been focused on limiting or eliminating such dendrite growth as batteries age over time; note: as conductive metal, surface plasmon electrons can be present on surfaces of Lithium nanostructures (more later)  Besides growing longer and then mechanically puncturing battery separators (causing internal short circuits), Lithium metal dendrites can great amplify local electric field strength on their very tips; this is called the “lightning rod effect.” Depending on exactly how high these fields get (determined by local current densities), they can locally break down battery materials and alter rates of nearby chemical redox and also “parasitic” reactions (explained later)  Dendrites are not the only type of conductive nanostructure that can cause problems with batteries; as we shall shortly see, even spherical nanoparticles (thought to be relatively safe by many battery technologists since they do not possess sharp asperities) can have very large local inhomogeneities in electric current density and amplification of electric field strengths on their surfaces. This is why metallic nanoparticle battery contaminants can be so troublesome  Electric fields close to surfaces of battery electrodes routinely reach static values of 109 to 1010 V/m; transient dynamic effects can briefly hit > 10x higher
  81. 81. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 81 Metallic dendrites can trigger thermal runaways in batteries Dendrites mechanically penetrate separators causing electrical shorts See 2015 Ph.D. thesis by Jens Steiger at Karlsruher Institut für Technologie Above: Lithium dendrites growing from an anode surface. Image from R. Chianelli in Jour. Cryst. Growth 34 pp. 239 - 244 (1976) http://d-nb.info/106673691X/34 Fig. 4(a). Lithium needles and faceted particles in “Mechanisms of dendrite growth in Lithium metal batteries” Credit: Jens Steiger (2015) Lithium needles grow into dendritic Lithium bushes
  82. 82. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 82 High local current densities may trigger Lithium plating Nadim Maluf, CEO of Qnovo, comments about Lithium metal growths http://qnovo.com/category/chemistry/ “On the left side, the surface of the graphite anode is pristine. On the right side, bright stripes of lithium metal are apparent on the edges. That’s where lithium metal tends to start forming - the current density on the edges tend to be higher (concentrated electric field lines) thus presenting favorable conditions for the formation of lithium metal. Additionally, manufacturing defects are more likely to be present on the edges, also presenting ‘seeds’ for plating. As the cell is further cycled (and aged), the lithium plating propagates and covers more of the anode surface, creating increased risks of a catastrophic failure.” Separator layer Separator layer
  83. 83. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 83 May grow inside batteries over time as result of cycling and aging Nanoparticle shapes locally intensify electric fields Surface plasmons are present on surfaces of metallic NPs embedded in oxides "Synthesis of spiky Ag-Au octahedral nanoparticles and their tunable optical properties” S. Pedireddy et al., J. Phys. Chem. C 117 pp. 16640 - 16649 (2013) http://pubs.acs.org/doi/abs/10.1021/jp4063077
  84. 84. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 84 Nanostructures of right shapes/compositions amplify electric fields Huge increase in local E-field strengths on nanoscale Details of nanoparticulate features on nm to μ length-scales are key to batteries Shows E-M field strength enhancement as a function of interparticle spacing Electric field enhancement at nano-antenna tip: R. Kappeler et al. (2007) Sharp tips exhibit so-called “lightning rod effect” by creating enormous local enhancement in electric field strengths Mandelbrot fractal Certain juxtapositions of tiny metallic nanoparticles at surfaces or interfaces can create local electric fields > 1011 V/m 108 x with 2 nm gap1011 x increase 1 nm = 10 Angstroms Electric fields at tips of atomic force microscopes (AFM) often reach 1011 V/m Dendrites are fractal structures Spherically shaped nanoparticles
  85. 85. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 85 Nanoparticle shapes/positioning redistribute E-fields E-fields extremely non-uniform across the surfaces of nanoparticles http://publications.lib.chalmers.se/records/fulltext/178593/local_178593.pdf Nanostructures may be present that briefly create pulsed E-fields > 2 x 1011 V/m “Electromagnetic field redistribution in hybridized plasmonic particle-film system” Y. Fang and Y. Huang Applied Physics Letters 102 pp. 153108 - 153111 (2013) “Combining simulation and experiment, we demonstrate that a metal nanoparticle dimer on a gold film substrate can confine more energy in the particle/film gap because of the hybridization of the dimer resonant lever and the continuous state of the film. The hybridization may even make the electric field enhancement in the dimer/film gap stronger than in the gap between particles. The resonant peak can be tuned by varying the size of the particles and the film thickness.” “By studying the electric field in the gaps A, B, and C (Figures 1(a) and 1(b)), we find that not only is the electric field in the gaps of a dimer-film system much stronger than in a single particle-film system (Figure 1(c)) but also, in a broad wavelength range, the E field in B is even stronger than in C. The maximum enhancement is more than 160 at 680 nm giving a SERS enhancement factor more than 6.5 x 108.” “Additional resonant modes are generated in a particle-film system by the hybridization between modes of particles and the continuous surface plasmon state of the film. These hybridized modes, which can be tuned by varying the size of particles and the thickness of the film, will lead to huge electric field enhancements in gaps between particles and film.”
  86. 86. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 86 Nanoparticle shapes/positioning redistribute E-fields Fang & Huang’s Figs. 1 and 3 show how electric fields are redistributed Conductive nanostructures can channel currents and amplify local electric fields Figure 1. Figure 3. Tiny red arrows show E-M energy flows across particle’s surface
  87. 87. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 87 Nanostructures can be antennas that absorb E-M energy SP electrons on nanoparticles can greatly intensify local electric fields Current surges can create attosecond E-fields > 2.5 x 1011 V/m on nanostructures E-M beam photons Sharp tips can exhibit “lightning rod effect” with large increases in local E-M fields Region of enhanced electric fields http://people.ccmr.cornell.edu/~uli/res_optics.htm Source of above image is Wiesner Group at Cornell University: “Plasmonic dye-sensitized solar cells using core-shell metal- insulator nanoparticles" M. Brown et al., Nano Letters 11 pp. 438 - 445 (2011) http://pubs.acs.org/doi/abs/10.1021/nl1031106 Graphics show capture of E-M photons and energy transfer via surface plasmon electrons
  88. 88. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 88 Surface E-field strength can alter chemical reaction rates Extremely high electric fields on electrode surfaces impacts chemistry Time-averaged electric fields inside active sites of enzymes can exceed 1010 V/m “Extreme electric fields power catalysis in the active site of ketosteroid isomerase” S. Fried et al., Science 346 pp. 1510 - 1514 (2014) http://web.stanford.edu/group/boxer/papers/paper303.pdf http://www.nature.com/nature/journal/v531/n7592/full/nature16989.html “Electrostatic catalysis of a Diels-Alder reaction” A. Aragonès et al. Nature 531 pp. 88 - 91 (March 3, 2016)  Recent work has shown that extremely strong electric fields found in active sites of biological enzymes and ordinary chemical catalysis can often play a very important if not pivotal role in accelerating rates of chemical reactions; see selected references below that concern electrostatic catalysis  By extension, large upward fluctuations in short-lived transient E-fields (for as little as attoseconds and as long as milliseconds) in nm to micron-scale regions on electrode surfaces in batteries could locally impact redox reaction rates, boost parasitic side-reactions, and on rare occasions, may even trigger LENRs  Key: evolution of nanostructures on aging electrode surfaces and how they may create inhomogeneities in local current density and electric field strengths
  89. 89. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 89 Idealized events for thermal runaway in Lithium-ion battery Local heating starts, breaks down nearby materials, and melts separator Severity of runaways varies greatly from shutdown of one cell to violent explosion http://www.extremetech.com/extreme/208888-doping-lithium-ion-batteries-could-prevent-overheating-and-explosion [SEI] [SEI]
  90. 90. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 90 Battery industry recognizes six causes of thermal runaways Internal shorts and propagation of thermal runaways are safety issues http://www.ntsb.gov/news/events/Documents/2013_Lithium_Batteries_FRM-Panel1d-Doughty.pdf “Failure mechanisms of Li-ion batteries” Dr. Daniel Doughty, Battery Safety Consulting, Inc. NTSB Battery Forum 12 MS-PowerPoint slides April 11, 2013
  91. 91. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 91 Battery industry definition of severe type of thermal runaway Field-failures appear to be spontaneous internal events inside batteries Not preceded by external abuse and no warning signs; violent with high temps Quoted from: “Batteries for Sustainability - Selected Entries from the Encyclopedia of Sustainability in Science and Technology” Ralph J. Brodd, ed., Chapter 9 by B. Barnett et al. “Lithium-ion Batteries, Safety” Springer ISBN 978-1-4614-5791-6 (2012) “Safety concerns have been heightened by highly publicized safety incidents and ensuing widespread recalls of Lithium-ion batteries used in laptop computers and cell phones. When these rare safety incidents occur, Lithium-ion batteries operating under otherwise normal conditions undergo what appear to be spontaneous [internal] thermal runaway events, often with violent flaming and extremely high temperatures. Moreover, these failures usually involve cells and cell designs that have passed extensive abuse testing, including the standardized abuse safety tests. Most such Li- ion safety incidents are not preceded by an obvious external abuse. We refer to these spontaneous safety incidents as field-failures’.”
  92. 92. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 92 Huge electric field gradients near battery electrode surfaces Fast surface physical changes can trigger charge separation/imbalances Large fluctuations of local E-field strength/current density in microscopic regions  Lattice strongly agrees with S. Harris & P. Lu’s (2013) insightful suggestion to battery technologists; namely that: “A detailed understanding of the electrode structures and inhomogeneities at all scales, from nano- to mesoscale (where inhomogeneities interact), can lead to an improved understanding of durability and failure mechanisms, ultimately leading to longer-lived batteries, with all their attendant advantages.”  Extremely high local electric fields - that is, from 1 x 1010 to > 2.5 x 1011 V/m for periods ranging from milliseconds down to attoseconds can cause a variety of problems inside batteries. Among other things, these vexing problems include exceeding electrical breakdown voltage of local materials, thus compromising the integrity of protective SEI layers and separators, triggering internal shorts  Lattice therefore believes that long-mysterious spontaneous internal electrical short circuits inside batteries that are widely thought to be one important cause of spontaneous field-failure thermal runaway events are likely to be rooted in transient inhomogeneities in local state of charge (SOC), dynamic charge distribution, current density, and/or electric field strength that can occur in nm to micron-scale regions on various types of nanostructures located in close physical proximity to surfaces of battery anodes or cathodes
  93. 93. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 93 Today’s safety abuse testing will not predict any field-failures So-called “field-failures” are often attributed to internal short circuits http://www.ntsb.gov/news/events/Documents/2013_Lithium_Batteries_FRM-Panel1d-Doughty.pdf “Failure mechanisms of Li-ion batteries” Dr. Daniel Doughty, Battery Safety Consulting, Inc. NTSB Battery Forum 12 MS-PowerPoint slides April 11, 2013
  94. 94. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 94 Tamer ‘garden variety’ of thermal runaways vs. field-failures Less extreme runaways well-understood; field-failures quite enigmatic Causes of less severe thermal runaways vs. field-failures not 100% identical ‘Garden variety’ thermal runaways: Field-failure thermal runaways:  Reasonably well understood  Triggered by substantial over-charging or excessively deep discharges; or,  Triggered by external mechanical damage to battery cells, e.g., crushing, punctures; internal dendrites can damage separators  Much rarer and comparatively poorly understood  Believed to be triggered by electrical arc discharges (internal shorts); but what causes initial nano-arcs?  Much higher peak temps versus ‘garden variety’ events  In addition to internal shorts, ultralow energy neutron reactions (LENRs) may be causative for an unknown %
  95. 95. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 95 Feng et al. aim for early detection of thermal runaways Mention “instantaneously triggered ISC” which occurs without warning “Online internal short circuit [ISC] detection for a large format lithium ion battery” X. Feng et al. Applied Energy 161 pp. 168 - 180 (2016) http://www.umich.edu/~racelab/static/Webpublication/2016-ENERGY-XuningF.pdf “It is identified that the abnormal depletion in the state-of-charge (SOC) and excessive heat generation associated with ISC affect the voltage and temperature responses … It is shown that the estimation algorithm can track the parameter variations in real-time, thereby making it feasible to track ISC incubation status or to detect [an] instantaneously triggered ISC.” “Although there is no clear explanation on what has led to ISC in [8,9], an abundance of evidences and field experiences indicate that it takes a long incubation time before an ISC strikes [12,13]. The ISC develops slowly during the incubation period as cycling continues [13]. The ISC-induced Joule heat will not develop into thermal runaway until the equivalent ISC resistance decreases to a substantially low level [13]. Before an ISC develops into a safety threat, it must be detected effectively to prevent the ensuing thermal runaway. The long time incubation makes it possible to perform early detection of ISC.”
  96. 96. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 96 Being driven to nm length-scales in a quest for higher energy density Technology domains converging at nanometer length-scales Technology domain Main purpose Source of energy Energy- scale Typical rates of reactions Temps in Centigrade Representative examples Electro- chemical batteries Store electrical energy reversibly in chemical bonds Chemical bonds Electron Volts (eV) Slow to moderate; typically diffusion rate-limited at various types of interfaces found inside batteries Li batteries can generally be operated safely only at temperatures <<< 100o C Large variety of different chemistries: lead-acid, alkaline, NiMH, Nickel- cadmium, Lithium-ion, LiFePO4, Lithium- oxygen, etc. Energetic materials Thermal igniters, explosives, propellants Chemical bonds eVs Fast combustion processes w. O2, e.g., deflagration and detonation Macroscopic peak temps max-out at ~5,000o C Thermite reactions (burning of metals), dinitro-chloro-azido benzene, RDX, etc. Ultralow energy neutron reactions (LENRs) Produce large amounts of CO2-free thermal energy from decay particles’ kinetic energies and gamma conversion to infrared Nuclear binding energy stored inside atomic nuclei Mega- electron Volts (MeVs) one MeV is equal to a million eVs Nuclear reactions themselves are super-fast, i.e., picosecond and faster; decays of any resulting unstable isotopes can range from very slow on order of millions of years to fast, i.e., nanoseconds Peak temperatures in micron- scale, short- lived LENR hotspot regions on surfaces and at interfaces typically reach ~4,000o to 6,000o C Neutron captures on various elements and isotopes; for example, LENR neutron capture processes starting with Lithium as base fuel target can release ~27 MeV in short sequence of nuclear reactions that do not release any energetic neutron or gamma radiation
  97. 97. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 97 Comparison of LENRs to fission and fusion power sources Heavy-element fission: involves shattering heavy nuclei to release stored nuclear binding energy; requires massive shielding and containment structures to handle radiation; major radioactive waste clean-up issues and costs; limited sources of fuel: today, almost entirely Uranium; Thorium-based fuel cycles now under development; heavy element U-235 (fissile isotope fuel) + neutrons  complex array of lower-mass fission products (some are very long-lived radioisotopes) + energetic gamma radiation + energetic neutron radiation + heat Fusion of light nuclei: involves smashing light nuclei together to release stored nuclear binding energy; present multi-billion $ development efforts (e.g., ITER, NIF, other Tokamaks) focusing mainly on D+T fusion reaction; requires massive shielding/containment structures to handle 14 MeV neutron radiation; minor radioactive waste clean-up $ costs vs. fission Two key sources of fuel: Deuterium and Tritium (both are heavy isotopes of Hydrogen) Most likely to be developed commercial fusion reaction involves: D + T  He-4 (helium) + neutron + heat (total energy yield 17.6 MeV; ~14.1 MeV in neutron) distinguishing feature is neutron production via electroweak reaction; neutron capture on fuel + gamma conversion to IR + decays [β , α] releases nuclear binding energy: early-stage technology; no emission of energetic neutron or gamma radiation and no long lived rad-waste products; LENR systems do not require massive and expensive radiation shielding and containment structures  much lower $$$ cost; many possible fuels: any element/isotope that can capture LENR neutrons; involves neutron-catalyzed transmutations of fuels into heavier stable elements that release heat Fission, fusion, and LENRs all involve controlled release of nuclear binding energy (heat) for power generation: no CO2 emissions; scale of energy release is MeVs (nuclear regime) > 1,000,000x energy density of chemical energy power sources Ultralow energy neutron reactions (LENRs): Fusion of light nuclei: Heavy element fission:
  98. 98. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 98 Lattice Energy LLC “There are known knowns; there are things we know that we know. There are known unknowns; that is to say, there are things that we now know we don't know. But there are also unknown unknowns – there are things we do not know we don't know.” Donald Rumsfeld U.S. Secretary of Defense Press conference (2002) April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 98 Laura13
  99. 99. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 99 Unrecognized rare heat producing process in batteries Ultralow energy neutron reactions (LENRs) may be occurring therein Hard radiation-free green reactions would not be recognized as a nuclear process Credit: ShutterstockLaura 13 April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 99
  100. 100. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 100 Widom-Larsen theory of ultralow energy neutron reactions Three key publications that begin in March of 2006 referenced below Many-body collective effects enable radiation-free green nuclear power “Ultra low momentum neutron catalyzed nuclear reactions on metallic hydride surfaces” A. Widom and L. Larsen European Physical Journal C - Particles and Fields 46 pp. 107 - 112 (2006) http://www.slideshare.net/lewisglarsen/widom-and-larsen-ulm-neutron- catalyzed-lenrs-on-metallic-hydride-surfacesepjc-march-2006 “A primer for electro-weak induced low energy nuclear reactions” Y. Srivastava, A. Widom, and L. Larsen Pramana - Journal of Physics 75 pp. 617 - 637 (2010) http://www.slideshare.net/lewisglarsen/srivastava-widom-and-larsenprimer-for- electroweak-induced-low-energy-nuclear-reactionspramana-oct-2010 “Nuclear abundances in metallic hydride electrodes of electrolytic chemical cells” A. Widom and L. Larsen Cornell physics preprint arXiv:cond-mat/0602472v1 (2006) http://arxiv.org/PS_cache/cond-mat/pdf/0602/0602472v1.pdf
  101. 101. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 101 Electroweak reaction in Widom-Larsen theory is simple Protons or deuterons react directly with electrons to make neutrons Need input energy source such as electricity to drive LENR neutron production EnergyE-field + e- sp g e-*sp + p+ g n0 + νe Collective many-body quantum effects: many electrons each transfer little bits of energy to a much smaller number of electrons also bathed in the very same extremely high local electric field Quantum electrodynamics (QED): smaller number of electrons that absorb energy directly from local electric field will increase their effective masses (m = E/c2) above key thresholds β0 where they can react directly with a proton (or deuteron) neutron and neutrino νe neutrinos: ghostly unreactive particles that fly-off into space; n0 neutrons capture on nearby atoms Neutrons + capture targets heavier elements + decay products Neutrons induce nuclear transmutations that release enormous amounts of clean, CO2-free heat Input energy creates electric fields > 2.5 x1011 V/m Heavy-mass e-* electrons react directly with protons electrons + protons (Hydrogen) g neutrons + neutrinos (benign particles, fly into space) Radiation-free LENR transmutation Require source(s) of input energy Many-body collective electroweak neutron production
  102. 102. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 102  Protons found within a wide variety of many-body condensed matter molecular systems spontaneously oscillate coherently and collectively; their quantum mechanical (Q-M) wave functions are thus effectively entangled with each other and also with nearby collectively oscillating, Q-M entangled surface plasmon or delocalized π electrons on aromatic rings and graphene; amazingly, this Q-M behavior occurs even in comparatively much smaller, simpler molecular systems, e.g. (NH4)2PdCl6, ammonium hexaclorometallate (see Krzystyniak et al., 2007 and Abdul-Redah & Dreismann, 2006)  While the e + p reaction is written on paper as a 2-body charged particle reaction, in condensed matter LENR active sites with entangled protons and electrons it is in fact a many-body reaction involving large numbers of charged particles. Absent many-body collective effects and quantum entanglement, it would take a temperature of ~10 billion degrees inside a collapsing star to drive the e + p reaction forward at substantial rates  Term (β - β0)2 in Widom & Larsen’s e + p reaction rate equation reflects the degree to which heavy-mass (renormalized) e-* electrons in a given LENR active site exceed the minimum threshold effective mass required for neutron production β0. Details are explained in our first principles ULE neutron production rates calculation preprint found on the Cornell arXiv: http://arxiv.org/PS_cache/nucl-th/pdf/0608/0608059v2.pdf  All other things being equal, the higher the μ-scale local density of e-*p+ reactants and the greater the rate and quantity of appropriate forms of nonequilibrium energy input, the higher will be the rate of ULE neutron production in nm- to μm-scale LENR-active sites found in failing batteries or in future LENR thermal power generation systems Widom-Larsen theory of ultralow energy neutron reactions Many-body collective effects and quantum entanglement key to LENRs
  103. 103. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 103 Input energy is required to trigger LENRs: to create non-equilibrium conditions that enable nuclear-strength local E-fields which produce populations of heavy- mass e-* electrons that react with many-body surface patches of p+, d+, or t+ to produce neutrons via e-* + p+ g 1 n or e-* + d+ g 2 n, e-* + t+ g 3 n (energy cost = 0.78 MeV/neutron for H; 0.39 for D; 0.26 for T); includes (can combine sources):  Electrical currents - i.e., an electron ‘beam’ of one sort or another can serve as a source of input energy for producing neutrons via e + p electroweak reaction  Ion currents - passing across a surface or an interface where SP electrons reside (i.e., an ion beam that can be comprised of protons, deuterons, tritons, and/or other types of charged ions); one method used for inputting energy is an ion flux caused by imposing a modest pressure gradient (Iwamura et al. 2002)  Incoherent and coherent electromagnetic (E-M) photon fluxes - can be incoherent E-M radiation found in resonant electromagnetic cavities; with proper momentum coupling, SP electrons can also be directly energized with coherent laser beams emitting photons at appropriate resonant wavelengths  Organized magnetic fields with cylindrical geometries - many-body collective magnetic LENR regime with direct acceleration of particles operates at very high electron/proton currents; includes organized and so-called dusty plasmas; scales-up to stellar flux tubes on stars with dimensions measured in kilometers Appropriate input energy is required to produce neutrons Electron or ion currents; E-M photon fluxes; organized magnetic fields
  104. 104. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 104 Summary of steps in Widom-Larsen theory of LENRs 5-step green process in sites occurs in 300 - 400 nanoseconds or less 1. Collectively oscillating, quantum mechanically entangled, many-body patches of Hydrogen (either +-charged protons or deuterons) will form spontaneously on metallic hydride surfaces or at certain types of interfaces, e.g. metal/oxide 2. Born-Oppenheimer approximation spontaneously breaks down, allows E-M coupling between local surface plasmon electrons and patch protons; application of input energy creates nuclear-strength local electric fields >2.5 x 1011 V/m - increases effective masses of surface plasmon electrons in patches 3. Heavy-mass surface plasmon electrons formed in many-body patches then react directly with electromagnetically interacting protons; process creates neutrons and neutrinos via many-body collective electroweak e + p reaction 4. Neutrons collectively created in patch have ultralow kinetic energies and are all absorbed locally by nearby atoms - no dangerous energetic neutron fluxes escape apparatus; any locally produced or incident gammas are converted directly into safe infrared photons (heat) by unreacted heavy electrons (Lattice patent US# 7,893,414 B2) - no hard MeV-energy gamma emissions 5. Transmutation of elements and formation of craters at active sites begins Collective many-body surface patches of protons can become LENR-active sites
  105. 105. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 105  For ~ 60 years, a body of theory has been developed and articulated to explain progressively increasing numbers of stable isotope anomalies observed in a vast array of mass spectroscopic data obtained from many different types of natural and experimental, abiological and biological systems. Central ideas in this chemical fractionation theory embody equilibrium as well as irreversible, mass-dependent, mass-independent, nuclear field shifts, and more recently “self-shielding” chemical processes claimed to be very able to separate isotopes, thus explaining reported isotopic anomalies  Although not explicitly acknowledged by fractionation theorists, an intrinsic bedrock fundamental assumption underlying all of this theory and interpretation of data is that nucleosynthetic processes capable of altering stable isotope ratios and/or producing new mixtures of different elements over time have not operated in such systems after the initial creation in stars; ergo, ordinary chemical processes are able to explain everything  If LENRs are occurring in some of these systems, the above-noted fundamental assumption will be violated LENR processes can mimic effects of chemical fractionation Theoretical chemists assume no nucleosynthesis occurs in their systems
  106. 106. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 106 Release of nuclear binding energy produces usable heat Several different mechanisms produce clean heat in LENR-active sites  Conceptually, LENR neutrons act like catalytic ‘matches’ that are used to ‘light the logs’ of target fuel nuclei. A neutron-catalyzed LENR transmutation network operates to release nuclear binding energy that has been stored and locked away in nuclei ‘fuel logs’ since they were originally produced at multi-million degrees in fiery nucleosynthetic processes of long-dead stars, many billions of years ago  LENR transmutation networks can produce copious heat that comes mainly from:  Direct conversion of gamma photons (γ) into infrared photons (IR) by heavy electrons; e.g., γ from neutron captures or β and other types of decays. IR is then scattered and absorbed by local matter, increasing its temperature (heat)  Nuclear decays of unstable neutron-rich isotopes that emit energetic particles (e.g., betas, alphas, protons, etc.); these particles then transfer their kinetic energy by scattering on local matter, which increases its temperature (heat)  Neutrino particles from weak interactions do not contribute to any production of excess heat; they will essentially bleed-off a small portion of released nuclear binding energy outward into space; unavoidable neutrino emissions are part of the energetic cost of obtaining energy releases in LENR networks from β - decays Widom-Larsen explains what generates calorimetrically measured excess heat
  107. 107. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 107 Needed to produce neutrons that induce transmutation of elements W-L theory explains creation of LENR-active sites Hydrogen (protons or deuterons) and heavy-mass electrons are key reactants Substantial quantities of Hydrogen isotopes must be brought into intimate contact with fully-H-loaded metallic hydride-forming metals (or non-metals like Se); e.g., Palladium, Platinum, Rhodium, Nickel, Titanium , Tungsten, etc. Please note that collectively oscillating, 2-D surface plasmon (SP) electrons are intrinsically present and cover the surfaces of such metals. At full lattice loading (saturation) of Hydrogenous isotopes, many-body, collectively oscillating island-like LENR active sites comprised of protons p+, deuterons d+, or tritons t+ will form spontaneously at random locations on surfaces Or, delocalized collectively oscillating π electrons comprising outer covering surfaces of fullerenes, graphene, benzene, and polycyclic aromatic hydrocarbon (PAH) molecules behave identically to SPs; when such molecules are hydrogenated, they create many-body, collectively oscillating, entangled quantum systems that per W-L theory are functionally equivalent molecular analogues of metal hydrides. In this case, LENRs are triggered on aromatic rings; strong tendency to transmute ring Carbons Born-Oppenheimer approximation breaks down in LENR active sites composed of nearly homogenous collections of collectively oscillating p+, d+, and/or t+ ions; enables E-M coupling between nearby SP or π electrons and hydrogen ions at active sites and creates nuclear-strength local electric fields > 2 x 1011 V/m. Effective masses of electrons in such E-fields are increased to multiple of an electron at rest (e → e*) determined by required ~simultaneous energy input(s); called “mass renormalization”
  108. 108. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 108 Widom-Larsen provides description for LENR-active sites  Per Widom-Larsen theory LENRs occur in localized micron- scale LENR-active sites on ~planar surfaces: at certain types of interfaces; or curved surfaces of various shaped nanoparticles  Tiny LENR-active sites live for less than ~300 - 400 nanoseconds before being destroyed by intense heat; local peak temps range from 4,000 - 6,000o C; LENR-active sites spontaneously reform under right conditions in well-engineered LENR thermal devices  Microscopic 100-micron LENR hotspot can release as much as several Watts of heat in < 400 nanoseconds; create crater-like features on surfaces that are visible in SEM images and show evidence for flash-boiling of both precious & refractory metals  Peak local LENR power density in microscopic LENR-active sites can hit > 1.0 x 1021 Joules/sec.m3 during brief lifetimes  Control macroscopic-scale temperatures in LENR systems by tightly regulating total input energy and/or total area/volumetric densities of LENR-active sites present in the reaction chambers Infrared video of LENR hotspots http://www.youtube.com/w atch?v=OUVmOQXBS68 LENR hotspots on Pd cathode Credit: P. Boss, U.S. Navy Size of these active sites ranges from 2 nanometers up to ~100+ microns Active sites have limited lifetimes before being destroyed by fast nuclear heating 100 μ LENR crater in Pd cathode LENR electrochemical cell Credit: P. Boss, U.S. Navy
  109. 109. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 109 W-L concept of a microscopic LENR-active surface site Comprised of many-body patches of protons and electrons on surface SP electrons and protons oscillate collectively and are mutually Q-M entangled Diameters of many-body active sites randomly range from several nm up to ~ 100+ microns + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + ‘Layer‘ of positive charge + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + - - - - - - - - - - - -- - - - - - - - - - - - - - - - - - - - - - - Thin-film of surface plasmon electrons - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Substrate: in example, is hydride-forming metal, e.g. Palladium (Pd); however, could just as easily be an Oxide (in that case, SP electrons would be only be present at nanoparticle-oxide interface, not across entire substrate surface as shown above) SP electron subsystem Substrate subsystem SP electron and proton subsystems form a many-body W-L active site; it can also reside on nanoparticles attached to surface Note: diagram components are not to scale Single nascent LENR-active site Proton subsystem Born-Oppenheimer approximation breaks down in this region + + + + + + + + + Many surface protons (hydrogen) + + + + + + + + + - - - - - - - - - - Many surface plasmon electrons - - - - -- - - - - -
  110. 110. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 110 Input energy creates high electric fields in LENR active sites Born-Oppenheimer breakdown enables nuclear-strength local E-field Huge electric field increase effective masses of some patch SP electrons Note: diagram components are not to scaleSubstrate subsystem Correct input energies create huge local E-fields > 2.5 x 1011 V/m between adjacent nanoparticles Substrate: in example, is hydride-forming metal, e.g. Palladium (Pd); however, could just as easily be an Oxide (in that case SP electrons would be only be present at nanoparticle-oxide interface, not across entire substrate surface as shown above) Nuclear-strength local electric fields created herein Input energyE-field + e- sp g e-*sp + p+ g n + νe [condensed matter surfaces] Single nascent LENR-active site + + + + + + + Many surface protons (hydrogen) + + + + + + + + + - - - - - - - - - - Many surface plasmon electrons - - - - -- - - - - -Nanoparticle Nanoparticle
  111. 111. April 14, 2016 Lattice Energy LLC, Copyright 2016 All rights reserved 111 LENRs occur in microscopic active sites found on surfaces Many-body collections of protons and electrons form spontaneously Ultralow energy neutrons produced & captured close to LENR-active sites + + + + + + + + + + + + + + + + + + + + + + + + + + + + Layer of positive charge + + + + + + + + ++ + + + + + + + + + + + + + + + Substrate subsystem - - - - - - - - - - -- - - - - - - - - - - - - -- - Thin-film of surface plasmon electrons - - - - - - - - - - - -- - - - - - - - - - - - - - Substrate: in this example, is hydride-forming metal, e.g. Palladium (Pd); could also be many other metals Note: diagram components are not to scale Input energy amplifies electric fields in local regions NPNP n + (Z, A) g (Z, A+1) [neutrons capture on nearby target atoms] (Z, A+1) g (Z + 1, A+1) + eβ - + νe [beta- decay] Often followed by β - decays of neutron-rich intermediate isotopic products = Metallic nanoparticle (NP) Intense heating in LENR-active sites will form μ-scale event craters on substrate surfaces After being produced, neutrons capture on targets in/around active sites

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